Unifying the 2eand 4e Reduction of Oxygen on Metal Surfaces

Venkatasubramanian Viswanathan, Heine Anton Hansen, Jan Rossmeisl, Jens K. Nørskov

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Understanding trends in selectivity is of paramount importance for multi-electron electrochemical reactions. The goal of this work is to address the issue of 2eversus 4e reduction of oxygen on metal surfaces. Using a detailed thermodynamic analysis based on density functional theory calculations, we show that to a first approximation an activity descriptor, ΔGOH*, the free energy of adsorbed OH*, can be used to describe trends for the 2e and 4e reduction of oxygen. While the weak binding of OOH* on Au(111) makes it an unsuitable catalyst for the 4e reduction, this weak binding is optimal for the 2e reduction to H2O2. We find quite a remarkable agreement between the predictions of the model and experimental results spanning nearly 30 years.

Original languageEnglish
JournalThe Journal of Physical Chemistry Letters
Issue number20
Pages (from-to)2948-2951
Publication statusPublished - 2012

Bibliographical note

© 2012 American Chemical Society. ACS AuthorChoice - This is an open access article published under an ACS AuthorChoice License, which permits copying and redistribution of the article or any adaptations for non-commercial purposes.


  • selectivity
  • activity volcano
  • electrocatalysis
  • fuel cells
  • hydrogen peroxide
  • lithium-air batteries


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